JPH09106102A - Toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner having excellent resistance against high temp. offset and having a wide temp. range for fixing adaptable for from a slow to fast fixing. SOLUTION: This toner contains at last a binder resin and a coloring agent. In this toner, a binder resin component (A) having 2000-50000mol.wt. and a binder resin component (B) having >100000mol.wt. separated by fractional liquid chromatography of the binder or the toner satisfy the relation of formula. In the formula, LMA is the weight average mol.wt. of the binder resin component (A), LMB is the weight average mol.wt. of the binder resin component (B), SA is the inertial radius of the binder resin component (A) and SB is the inertial radius of the binder resin component (B), all measured by a light scattering method.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner used in image forming methods such as electrophotography, electrostatic recording and electrostatic printing.

[0002]

2. Description of the Related Art Conventionally, as an electrophotographic method, U.S. Pat. No. 2,297,691 and JP-B-42-23910 are known.
Numerous methods are known as described in Japanese Patent Application Laid-Open Publication No. Hei. Generally, a photoconductive substance is used to form an electric latent image on a photoconductor by various means, and then the latent image is developed with a toner, and a toner image is formed on a transfer material such as paper if necessary. After transfer, the toner is fixed by heating, pressure, heating and pressurizing, or solvent vapor to obtain a toner image.

Various methods and apparatuses have been developed for fixing the toner image to a sheet such as paper, which is the above-mentioned final step, but the most common method at present is a pressure heating method using a heat roller.

In the pressure heating method using a heating roller, the toner image is fixed by passing the surface of the heat roller having a releasing property to the toner and the toner image surface of the sheet to be fixed while pressing the sheet under pressure. Is performed. In this method, the surface of the heat roller and the toner image on the sheet to be fixed come into contact with each other under pressure, so that the thermal efficiency at the time of fusing the toner image on the sheet to be fixed is extremely good, and quick fixing is required. You can

However, at present, different toners are used depending on the model of copying machine or printer. This is mainly due to the difference in fixing speed and fixing temperature. The heating roller surface and the toner image are in a molten state,
Due to the contact under pressure, a part of the toner image adheres to and transfers to the surface of the fixing roller, retransfers to the next sheet to be fixed, and stains the sheet to be fixed.The so-called offset phenomenon affects the fixing speed and temperature. This is because it will be greatly received. Generally, when the fixing speed is low, the heating roller surface temperature is low, and when the fixing speed is high, the heating roller surface temperature is high. This is because the amount of heat given to the toner by the heating roller for fixing the toner is made substantially constant regardless of the fixing speed.

However, since the toner on the sheet to be fixed forms several toner layers, the fixing speed is particularly high, and in a system where the heating roller temperature is high, the toner layer contacting the heating roller and the fixing layer are fixed. When the heating roller temperature is high, the top layer toner causes an offset phenomenon because the temperature difference of the lowermost toner layer that is in contact with the sheet is very large, and when the heating roller temperature is low. Since the toner in the lowermost layer is not sufficiently melted, the toner is not fixed to the sheet to be fixed and a phenomenon of low temperature offset occurs.

As a method for solving this problem, when the fixing speed is high, a method of increasing the pressure at the time of fixing to anchor the toner to the fixing target sheet is usually used. With this method, the temperature of the heating roller can be lowered to some extent, and the high temperature offset phenomenon of the uppermost layer toner can be prevented. However, since the shearing force applied to the toner becomes extremely large, the sheet to be fixed winds around the fixing roller, so-called winding offset, and after separation of the member separating the sheet to be fixed from the fixing roller appears in the image. In addition, since the pressure is high, the line image is crushed during fixing and the toner flies off, so that the image quality of the copy image is likely to deteriorate.

Therefore, in high-speed fixing, generally, a toner having a lower melt viscosity than that in low-speed fixing is used, and the heating roller temperature and the fixing pressure are lowered to fix the toner while preventing high-temperature offset and winding offset. However, when such a toner having a low melt viscosity is used for low-speed fixing, an offset phenomenon occurs at a high temperature because of the low viscosity.

Therefore, in the present situation, there is no toner having a wide fixing temperature range which can be applied from low speed to high speed and which is excellent in offset resistance.

Furthermore, in recent years, it has been desired to improve the image quality of copied images by digitizing copying machines and making toner particles finer. In other words, it is required that in a photographic image containing characters, the characters of the copied image are clear and the photographic image has density gradation that is faithful to the original. Generally, in copying a photographic image containing characters, if the line density is increased to make the characters clear, not only the density gradation of the photographic image is impaired, but also the image becomes very rough in the halftone portion.

Further, as described above, the line image is crushed or skipped at the time of fixing, so that the image quality of the copy image is deteriorated.

Further, when the line density is increased, the amount of the toner adhered is large in the toner transfer step, so that the toner is pressed against the photoconductor and adheres to the photoconductor during the transfer, and the toner on the line is lost. A so-called hollow image phenomenon occurs, resulting in a low quality copy image. On the other hand, if an attempt is made to improve the density gradation of the photographic image, the density of the character line will decrease and the sharpness will deteriorate.

Further, although the resolution and the sharpness of the image can be improved by reducing the particle size of the toner, various problems occur.

First of all, as the toner particle size is reduced, the fixability of the halftone portion becomes worse. This phenomenon is particularly remarkable in high-speed fixing. This is because the toner amount in the halftone portion is small, the toner transferred to the concave portion of the fixing sheet has a very small amount of heat applied from the heating roller, and the fixing pressure is also suppressed by the convex portion of the fixing sheet. It will be worse because of Also, the toner transferred to the convex portion of the fixing target sheet in the halftone portion is
Since the toner layer thickness is thin, the shearing force applied to each toner particle is much larger than that of the solid black portion where the toner layer thickness is thick, and an offset phenomenon occurs or a copy image with low image quality is obtained.

Further, there is a problem of fog. By reducing the particle size of the toner, the surface area of the toner is increased, and therefore, the width of the charge amount distribution is increased, and fogging is likely to occur. Further, as the toner surface area increases, the charging characteristics of the toner are more likely to be affected by the environment.

It is also apparent that when the toner particle size is reduced, the dispersion state of the magnetic substance and the colorant has a great influence on the charging property of the toner.

When such a small particle size toner is applied to a high-speed copying machine, especially under low humidity, excessive charging may occur, resulting in fog and a decrease in density.

Further, in the multifunctionalization of the copying machine, for example, a part of an image is erased by exposure or the like, and then another image is inserted into the part to perform multiple multicolor copying, or copy paper. With the function of removing the frame around the frame, fogging occurs in a portion to be whitened on the image.

That is, when an image is erased by applying a potential having a polarity opposite to the latent image potential with respect to the development reference potential with strong light such as an LED or a fuse lamp, there is a problem that the fog tends to occur at that portion. .

At present, there is no toner that solves the above various problems.

[0021]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner which solves the above problems.

An object of the present invention is to provide a toner excellent in offset resistance without impairing the fixing property from low speed to high speed copying machines.

The object of the present invention is to provide excellent fixability in the halftone portion and to obtain a copy image of good image quality, even if the particle size is reduced or the particle size is reduced, from low speed to high speed copying machines. To provide toner.

An object of the present invention is to provide a toner capable of obtaining a high-density copy image without fog from low speed to high speed copying machines.

An object of the present invention is to provide a toner which gives good images even under low humidity and high humidity without being affected by environmental changes.

An object of the present invention is to provide a toner which gives a stable and good image even in a high-speed machine and has a wide range of applicable models.

An object of the present invention is to provide a toner which is excellent in durability, has a high image density even when it is continuously used for a long time, and can obtain a copy image without white background fog.

An object of the present invention is to provide a toner in which, in a photographic image containing characters, the characters of the copied image are clear and the photographic image has density gradation that is faithful to the original.

[0029]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner containing at least a binder resin and a colorant, in which the molecular weight of the binder resin or the toner fractionated by preparative liquid chromatography is The binder resin component A in the region of 2000 to 50000 and the binder resin component B in the region of 100,000 or more in molecular weight are represented by the following formula (1).

[0030]

(Equation 2) (In the formula (1), LM _A represents the weight average molecular weight of the binder resin component A measured by the light scattering method, and LM _B is the weight average molecular weight of the binder resin component B measured by the light scattering method. , S _A represents the radius of gyration of the binder resin component A measured by the light scattering method, and S _B represents the radius of gyration of the binder resin component B measured by the light scattering method). It is achieved by a toner characterized in that

This is due to the following reasons.

LM in equation (1)_A/ S _A ^Three, LM_B/ S
_B ^ThreeIndicates the weight average molecular weight per unit volume.
I have. Polymer having linear polymer () and branched chain
The weight average molecular weight measured by the light scattering method in () is approximately
Linear polymers in formula (1) when they are almost identical
Branch with the weight average molecular weight and radius of gyration of () as the denominator
Weight average molecular weight of polymer having chain (), radius of gyration
N obtained by putting the value of_{■ 2 / ■ 1}■, ■■■■■■■
■ Limmer (■ 2) ■■■■■■■■■■■■■■■■ Parameter ■
■■. ■ (1) ■■■■■ Limmer B ■■■■■■■■, ■■■■
■■■■■■, ■ Rimmer A ■■■■■■■■, ■■■■■■■
■■■■■■■■■ n_{A / B}Of polymer A and polymer B
It is a parameter that indicates the ratio of the degree of branching.

A polymer having a large number of branches has a smaller radius of gyration and a lower viscosity than a polymer having the same molecular weight and a small number of branches. The present inventors have found that a low molecular weight component (a molecular weight of 20
Binder resin component A of 0 to 50000 and high molecular weight component (molecular weight of 1000 separated by preparative liquid chromatography)
The ratio of the degree of branching with the binder resin component B) of 00 or more is 1 to 10
It has been found that the binder resin or toner at 0 has a lower viscosity and can be further fixed at low temperature.

In the present invention, the low molecular weight component (binder resin component A) is defined as the region having a molecular weight of 2000 to 50000, which is fractionated by means of a preparative liquid chromatograph. The reason is as follows.

The component having a molecular weight of less than 2000, which has been fractionated by preparative liquid chromatography, particularly when it is a polyester resin, is likely to be a monomer bound to a quantity. This is because there is a high possibility that the polymer does not have the desired branched chain.

The reason why the upper limit of the molecular weight of the binder resin component A is 50,000 is due to the following reason.
The inventors of the present invention investigated the polymer having a molecular weight of more than 50,000 by preparative separation by preparative liquid chromatography, and found that the melt viscosity sharply increased as compared with the polymer having a molecular weight of 50,000 or less. ,
This is because it was feared that the fixability would be impaired.

In the present invention, the high molecular weight component (binder resin component B) is defined as a region having a molecular weight of 100,000 or more, which is fractionated by preparative liquid chromatography. The reason is as follows.

The present inventors have found that a polymer having a molecular weight of more than 50,000 and less than 100,000 and a molecular weight of 1 are used.
This is because, when polymers having a molecular weight of 100,000 or more were examined by fractionation, it was found that the polymers having a molecular weight of 100,000 or more had particularly good elasticity. Then, the present inventors examined the relationship between the degree of branching between the binder resin component A (low molecular weight component) and the binder resin component B (high molecular weight component) to obtain good fixability and offset resistance. They have invented an excellent binder resin.

When n _{A / B} is less than 1, the number of branches of the binder resin component B, which is a high molecular weight component, is greater than that of the binder resin component A, which is a low molecular weight component. It becomes difficult for A to be incorporated into the binder resin component B. Therefore, the branching of the low molecular weight component (binder resin component A) becomes smaller than the branching of the high molecular weight component (binder resin component B).
The viscosity as a resin tends to increase, and the fixing property tends to deteriorate when used as a toner.

When n _{A / B} is larger than 100,
The binder resin component A, which is a low molecular weight component, is incorporated in the binder resin component B, which is a high molecular weight component, but the degree of branching of the binder resin component A is very high, and therefore the low molecular weight component (binder resin component Since the branching of the component A) becomes larger than the branching of the high molecular weight component (binder resin component B), the viscosity as a resin tends to be excessively reduced, and the high temperature offset resistance when used as a toner is high. It tends to get worse.

From the above, it is desirable that n _{A / B} in the formula (1) is in the range of 1-100, preferably 2-70.

Here, in the formula (1), a low molecular weight component (binder resin component A) having a weight average molecular weight measured by a light scattering method in a region of a molecular weight of 2000 to 50000, which is fractionated by a preparative liquid chromatograph. N of the linear polymer component (O ₁ ) and the binder resin component A, which are almost the same as
_{A / O 1} is 1.2 or more, preferably 1.5 or more, and the weight average molecular weight measured by a light scattering method in a region where the molecular weight fractionated by preparative liquid chromatography is 100,000 or more is high. N _B determined from the values of the weight average molecular weight and the radius of gyration of the linear polymer component (O ₂ ) which is almost the same as the molecular weight component (binder resin component B) and the binder resin component B measured by the light scattering method. _{/ O 2} is preferably from 1 to 30, preferably from 1 to 20, in accordance with the object of the present invention. Where LM / S
^{Since 3} is affected by the molecular weight, the linear polymer component (O) used should be in the molecular weight range of the binder resin components A and B.

Further, the binder resin component A and the binder resin component B
Branched chain weight average molecular weights Mb _A and Mb _B of 300 to 800
It is preferably 00, preferably 500 to 50,000. Further, it is desirable that Mb _A / Mb _B is 0.01 or more, preferably 0.05 or more.

This is the branched chain weight average molecular weight Mb _A , M
When b _B is less than 300, there is almost no viscosity lowering effect due to branching, and when it exceeds 80,000, the branched chain causes the radius of gyration to become very large, which is not suitable for the purpose of the present invention. Becomes Also, Mb _A / Mb _B is 0.0
Even when it is less than 1, there is almost no viscosity lowering effect due to branching as described above, which is not suitable for the purpose of the present invention.

Further, the glass transition temperature Tg of the binder resin component A and the binder resin component B is 50 to 80 ° C., preferably 5
It is preferably 3 to 70 ° C. This has a Tg of 50
This is because if the temperature is lower than 0 ° C, fusion of the photoreceptor may occur or the storage stability is poor, and if it is higher than 80 ° C, the fixing property is poor.

As a method for lowering the viscosity, a method of lowering the glass transition temperature of the polymer or lowering the molecular weight is usually mentioned. However, the former method has poor storage stability, and the latter method has drawbacks such as deterioration in high temperature offset resistance and charging characteristics, and further fusion to a photoreceptor. In addition, as a method for increasing the degree of branching in vinyl resins, JP-A-3-87753 and JP-A-3-2037 are known.
The method of using a macromonomer in Japanese Patent Laid-Open No. 46 is disclosed in Japanese Patent Laid-Open No.
No. 24648 discloses a method using an ε'-caprolactone-modified hydroxyvinyl monomer.
However, when many macromonomers are used to increase the degree of branching by these methods, the glass transition temperature of the resin is lowered and the storage stability is deteriorated. In order to maintain good storage stability, the molecular weight of the main chain is increased to increase the glass transition temperature of the main chain, or the monomer composition of the main chain is changed,
There is a method of increasing only the glass transition temperature without changing the molecular weight. However, with either of these methods, the fixing temperature rises, and the effect of low-temperature fixing by increasing the branching degree does not appear. This is because the composition distribution of macromonomers in the polymer is greatly affected, and when many macromonomers are polymerized in the polymer chain, this polymer deteriorates storage stability. Therefore, in order to improve the storage stability of this polymer, the glass transition temperature of the main chain must be increased excessively for some polymers in which many macromonomers are unevenly distributed, and as a result, Fixability deteriorates. That is, the glass transition temperature (Tgs) in the main chain and the glass transition temperature (T
Since gb) is so different, the viscosity-lowering effect due to branching is offset by the increase in viscosity due to the increase in the glass transition temperature of the main chain. Therefore, in the present invention, the range of | Tgs-Tgb | ≦ 30 deg, preferably | Tgs-Tgb | ≦ 20 deg is preferable.

Further, in the polyester resin, as a method for increasing the degree of branching, a method of using a carboxylic acid or alcohol having a valence of 3 or more, or a method of using a dicarboxylic acid having a side chain or a diol is disclosed in JP-A-59-59. -2286
No. 58, JP-A No. 62-195678, and the like. Since the side chains of the dicarboxylic acids and diols having a side chain used herein are aliphatic side chains, this side chain has the same glass transition temperature as that described for the vinyl resin. The effect of lowering the viscosity by decreasing the degree of branching and increasing the degree of branching is lost by increasing the glass transition temperature of the main chain. Further, in the method using a trivalent or higher carboxylic acid or alcohol, the degree of branching is certainly high, but this is because the degree of branching for high molecular weight is increased,
The degree of branching for low molecular weight does not increase. That is, even in this case, the composition distribution is similar to that of the vinyl resin, and the low molecular weight component and the high molecular weight component have different compositions.

Further, JP-A-63-225244-22
Japanese Patent No. 5246 discloses a method in which two kinds of non-linear polyesters having different softening points are blended and used. However, it does not suggest the relationship between the weight average molecular weight and the radius of gyration measured by the light scattering method of the binder resin component A and the binder resin component B separated by the preparative liquid chromatograph in the present invention. Furthermore, the polyester production method is also different from that of the present invention, in which the acid and alcohol are charged first. In the present invention, polyester is synthesized by the method described below in order to adjust the degree of branching.

Further, for the purpose of improving the fixing property, JP-A-5-
Japanese Patent No. 249736 discloses a method of using a resin composed of high-density crosslinked microgel particles containing a linear portion and a crosslinked portion. In the present invention, there is a cross-linking portion,
It does not have a microgel structure.

As a result of intensive studies, the present inventors have found that the degree of branching and the molecular weight of the branched chain in the low molecular weight component and the high molecular weight component,
Furthermore, the control method of the branched glass transition temperature was found.

For the vinyl resin, for example, a method of previously synthesizing a branched polymer having a double bond at the terminal and adding the branched polymer at the time of polymerizing the main chain polymer can be mentioned. The branched polymer having a double bond at the terminal can be synthesized by anionic polymerization, photopolymerization method or the like. More preferably, in order to make the composition distribution uniform, it is desirable to add the monomer several times during the polymerization reaction.

As the vinyl resin, a resin synthesized by using a monomer having 3 or more vinyl groups can be used.

In the polyester resin, for the low molecular weight polyester, for example, a carboxylic acid or alcohol having a valence of 3 or more is used, and the condensation reaction is stopped before a gel is formed to obtain a low molecular weight component; or 3 A method for obtaining a low molecular weight component by stopping the condensation reaction before forming a gel by using 10 mol% or more of a carboxylic acid or alcohol having a valence of 3 or more; or after synthesizing a linear polyester having a low molecular weight, a carboxylic acid or an alcohol having a valence of 3 or more Is added and polycondensation is further carried out. For the high molecular weight polyester, a low molecular weight component and a high molecular weight component of a linear polyester are previously synthesized, and when these are mixed, a carboxylic acid or alcohol having a valence of 3 or more is further added to form a branched chain. Create a polymer with a lot of content. By mixing the low molecular weight polyester and the high molecular weight polyester, the binder resin of the preferred embodiment of the present invention is obtained.

Further, in the present invention, gel permeation chromatography (GP) of the toner or the binder resin is used.
In the molecular weight measurement by the C method), the molecular weight is 2000-5.
It is necessary that the abundance ratio in the GPC chromatogram in the region of 0000 is 50 to 90%. This is an essential component for imparting viscosity as a toner property and improving fixability. When the abundance ratio in the GPC chromatogram in the molecular weight range of 2000 to 50000 is less than 50%, the viscosity as a toner becomes weak, and the fixability becomes poor especially in a high speed copying machine. Also, the molecular weight is 20
If the abundance ratio in the GPC chromatogram in the region of 0 to 50000 exceeds 90%, the viscosity of the toner becomes too strong, and the high temperature offset resistance and scorching resistance offset level deteriorate. As described above, in the molecular weight measurement by the GPC method, the form of the binder resin or toner of the present invention is an important point for improving the fixability and offset resistance.

[0055]

BEST MODE FOR CARRYING OUT THE INVENTION The binder resin for toner used in the present invention includes vinyl resins, polyester resins, epoxy resins and the like. Among them, vinyl resins and polyester resins are fixative and charging characteristics. Is more preferable.

Examples of vinyl resin monomers include the following.

For example, styrene, o-methylstyrene, m
-Methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene,
2,4-dimethylstyrene, pn-butylstyrene,
Styrene and its derivatives such as p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene and pn-dodecylstyrene; ethylene, Ethylenically unsaturated monoolefins such as propylene, butylene, isobutylene; Unsaturated diolefins such as butadiene; Vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride; Vinyl acetate, vinyl propionate, Vinyl ester acids such as vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate. , Α-methylene aliphatic monocarboxylic acid esters such as phenyl tacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, acrylic Acid n-octyl, dodecyl acrylate,
Acrylic esters such as 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; vinyl methyl ether,
Vinyl ethers such as vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone N-vinyl compound; vinylnaphthalene; acrylic acid or methacrylic acid derivative such as acrylonitrile, methacrylonitrile, acrylamide;
Examples thereof include esters of unsaturated acids and diesters of dibasic acids.

Further, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenylsuccinic acid, fumaric acid and mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenylsuccinic anhydride Unsaturated dibasic acid anhydrides such as: maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl ester Half ester of unsaturated dibasic acid such as half ester, alkenylsuccinic acid methyl half ester, fumaric acid methyl half ester, mesaconic acid methyl half ester; unsaturated dibasic acid ester such as dimethyl maleic acid, dimethyl fumaric acid; Acid, methacrylic acid, crotonic acid, such as cinnamic acid alpha, beta-unsaturated acid; crotonic acid anhydride, such as alpha of cinnamic acid anhydride, beta-unsaturated acid anhydride, the alpha, beta
-Anhydrides of unsaturated acids and lower fatty acids; and monomers having a carboxyl group such as alkenyl malonic acid, alkenyl glutaric acid, alkenyl adipic acid, acid anhydrides and monoesters thereof.

Further, as the monomer for leaving a double bond at the terminal of the branched chain polymer synthesized in advance in the present invention, unsaturated diolefins such as butadiene and isoprene, and polymerizable vinyl such as divinylbenzene and divinylnaphthalene are used. Examples thereof include monomers having two or more groups.

Further, as the monomer having three or more vinyl groups used in the present invention, Si (CH = CH
₂ ) ₄ (Tetravinylsilane), (H ₂ C = CH) ₄ S
_n (tetravinyltin), C ₆ H ₉ (CH = CH ₂ )
₃ (1,2,4-trivinylcyclohexane) and the like can be mentioned.

The vinyl-based resin used in the present invention preferably has at least one peak in the molecular weight range of 2000 to 100,000 and at least one peak in the 100,000 or more region in the molecular weight distribution measurement by GPC method. It is desirable to have one.

The glass transition temperature of this vinyl resin is 50 to 80 ° C., preferably 53 to 70 ° C.

In the present invention, a homopolymer or copolymer of a vinyl monomer, polyester, polyurethane,
Epoxy resin, polyvinyl butyral, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, etc. may be used by mixing with the above-mentioned binder resin if necessary. it can.

The following are examples of the monomers of the polyester resin used in the present invention.

As the alcohol component, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol,
1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, and a bisphenol derivative represented by the formula (A);

[0066]

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Further, diols represented by the formula (b);

[0068]

Embedded image And the like.

As the divalent carboxylic acid, benzenedicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and phthalic anhydride or their anhydrides; alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid. Or an anhydride thereof, and further having 6 to 1 carbon atoms
Examples include succinic acid substituted with an alkyl group of 8 or its anhydride; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, itaconic acid, and their anhydrides.

Further, glycerin, pentaerythritol, sorbit, sorbitan, and polyhydric alcohols such as oxyalkylene ether of novolac type phenol resin; trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their anhydrides, etc. And the like.

The glass transition temperature of the polyester resin used in the present invention is 50 to 80 ° C., preferably 53 to 70.
And the number average molecular weight Mn by the GPC method is 1
000-80,000, preferably 1500-5000
0, the weight average molecular weight Mw by GPC method is 5000 to 1
It is × 10 ⁷ , preferably 1 × 10 ^{4 to} 5 × 10 ⁶ .

The acid value of the polyester resin is 2 to 7
It is 0 and the OH value is preferably 50 or less. Outside this range, the polarity is strong and is affected by the environment (temperature and humidity), so that the chargeability of the toner becomes extremely poor.

In the toner of the present invention, a charge control agent can be used, if necessary, in order to further stabilize its chargeability. The charge control agent is 0.1% by weight per 100 parts by weight of the binder resin.
It is preferable to use 1 to 10 parts by weight, preferably 0.1 to 5 parts by weight.

Charge control agents known in the art today include the following:

To control the toner to be negatively charged,
For example, organic metal complexes and chelate compounds are effective. Examples thereof include a monoazo metal complex, an aromatic hydroxycarboxylic acid, a metal complex, and an aromatic dicarboxylic acid-based metal complex. Others include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters,
Phenol derivatives of bisphenol are mentioned.

When a positively chargeable toner is prepared, nigrosine, a triphenylmethane compound, a rhodamine dye, polyvinyl pyridine or the like may be used as the charge control agent exhibiting the positive chargeability. Further, in the case of producing a color toner, 0.1 to 40 mol%, preferably 1 to 3 mol%, of an aminocarboxylic acid-containing ester such as dimethylaminomethyl methacrylate having a positive charging property as a monomer.
Use a binder resin containing 0 mol%, or
A colorless or light-colored positive charge control agent that does not affect the color tone of the toner may be used. Examples of the positive charge control agent include quaternary ammonium salts represented by structural formulas (A) and (B).

[0077]

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[0078]

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Among the quaternary ammonium salts represented by the structural formulas (A) and (B), the positive charge control agent represented by the structural formulas (A) -1 and -2 and the structural formula (B) -1 is used. Are preferable because they show good chargeability with little environmental dependence.

[0080]

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[0081]

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[0082]

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In the case of using an aminocarboxylic acid-containing ester such as dimethylaminomethyl methacrylate, which exhibits positive charging characteristics, as the resin component of the binder resin in the positive charging toner, a positive charge control agent or a negative charge control agent is used. Use as needed.

In the case where the positively chargeable toner does not use an aminocarboxylic acid-containing ester such as dimethylaminomethyl methacrylate, which exhibits positively charging characteristics as a resin component, the positive charge control agent is 0 per 100 parts by weight of the binder resin. 1-1
It is desirable to use 5 parts by weight, preferably 0.5 to 10 parts by weight. Further, when the aminocarboxylic acid-containing ester is used, a positive charge control agent and / or a negative charge control agent may be added to 100 parts by weight of the binder resin for the purpose of providing good chargeability with little environmental dependence. It is desirable to use 0 to 10 parts by weight, preferably 0 to 8 parts by weight.

When the toner of the present invention is used as a magnetic toner, the magnetic material contained in the magnetic toner includes iron oxides such as magnetite, maghemite and ferrite, and iron oxides containing other metal oxides; Fe, Co and Ni. Like metals, or these metals and Al, Co, Cu, P
b, Mg, Ni, Sn, Zn, Sb, Be, Bi, C
Alloys with metals such as d, Ca, Mn, Se, Ti, W, and V, and mixtures thereof, and the like.

Conventionally, as a magnetic material, triiron tetraoxide (F) has been used.
e ₃ O ₄ ), iron sesquioxide (γ-Fe ₂ O ₃ ), zinc iron oxide (ZnFe ₂ O ₄ ), yttrium iron oxide (Y ₃ Fe
₅ O ₁₂ ), iron cadmium oxide (CdFe ₂ O ₄ ), iron gadolinium oxide (Gd ₃ Fe ₅ —O ₁₂ ), iron oxide copper (CuF)
e ₂ O ₄ ), lead iron oxide (PbFe ₁₂ —O ₁₉ ), iron nickel oxide (NiFe ₂ O ₄ ), iron neodymium oxide (NdFe)
₂ O ₃ ), barium iron oxide (BaFe ₁₂ O ₁₉ ), iron magnesium oxide (MgFe ₂ O ₄ ), iron manganese oxide (MnF
e ₂ O ₄ ), iron lanthanum oxide (LaFeO ₃ ), iron powder (F
e), cobalt powder (Co), nickel powder (Ni) and the like are known, but according to the present invention, the above magnetic materials are used alone or in combination of two or more kinds. Particularly preferred magnetic materials for the purposes of the present invention are fine powders of iron tetroxide or γ-iron sesquioxide.

These ferromagnetic materials have an average particle size of 0.1 to 2
about 10 μm, the magnetic characteristics when a 10K Oersted is applied show a coercive force of 20 to 150 Oersted saturation magnetization of 50 to 200 e
mu / g (preferably 50 to 100 emu / g) and a residual magnetization of 2 to 20 emu / g are desirable.

For 100 parts by weight of the binder resin, the magnetic material 1
It is preferable to use 0 to 200 parts by weight, preferably 20 to 150 parts by weight.

Carbon black, titanium white, and any other pigments and / or dyes can be used as the colorant regardless of whether it is a single component or a two component. For example, when the toner of the present invention is used as a magnetic color toner, C.I. I. Direct Red 1,
C. I. Direct Red 4, C.I. I. Acid Red 1, C.I. I. Basic Red 1, C.I. I. Modant Red 30, C.I. I. Direct Blue 1, C.I. I. Direct Blue 2, C.I. I. Acid Blue 9, C.I.
I. Acid Blue 15, C.I. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I. Modant Blue 7, C.I. I. Direct Green 6, C.I. I. Basic Green 4, C.I. I. Basic Green 6 and the like. Examples of pigments include: graphite, cadmium yellow, mineral fast yellow, navel yellow, naphthol yellow S, Hansa yellow G, permanent yellow NCG, tartrazine lake, red-mouthed graphite, molybdenum orange, permanent orange GTR, pyrazolone orange, benzidine orange G , Cadmium Red, Permanent Red 4R, Watching Red Calcium Salt, Eosin Lake, Brilliant Carmine 3B, Manganese Purple, Fast Violet B, Methyl Violet Lake, Navy Blue, Cobalt Blue, Alkaline Blue Lake, Victoria Blue Lake, Phthalocyanine Blue,
First Sky Blue, Indanthrene Blue BC,
Chrome green, chromium oxide, pigment green B,
Malachite Green Lake, Final Yellow Green G, etc.

When the toner of the present invention is used as a two-component full-color toner, the following may be mentioned. Examples of magenta color pigments include C.I. I. Pigment Red 1,2,3,4,5,6,7,8,9,1
0, 11, 12, 13, 14, 15, 16, 17, 1
8, 19, 21, 22, 23, 30, 31, 32, 3
7, 38, 39, 40, 41, 48, 49, 50, 5
1,52,53,54,55,57,58,60,6
3,64,68,81,83,87,88,89,9
0, 112, 114, 122, 123, 163, 20
2,206,207,209, C.I. I. Pigment Violet 19, C.I. I. Butt Red 1,2,10,1
3, 15, 23, 29, 35 and the like.

Although such a pigment may be used alone, it is more preferable from the viewpoint of the image quality of a full-color image to improve the sharpness by using a dye and a pigment together. Examples of such magenta dyes include C.I. I. Solvent Red 1,
3, 8, 23, 24, 25, 27, 30, 49, 81,
82, 83, 84, 100, 109, 121, C.I. I.
Disperse Red 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27, C.I. I. Oil-soluble dyes such as Disperse Violet 1, C.I. I. Basic Red 1,2,9,12,13,14,15,17,18,
22, 23, 24, 27, 29, 32, 34, 35, 3
6, 37, 38, 39, 40, C.I. I. Basic Violet 1,3,7,10,14,15,21,25
And basic dyes such as 26, 27 and 28.

Other coloring pigments include cyan pigments such as C.I. I. Pigment Blue 2, 3, 15,
16, 17, C.I. I. Bat Blue 6, C.I. I. Acid Blue 45 or a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on a phthalocyanine skeleton having a structure represented by Chemical Formula 3.

[0093]

Embedded image

As the coloring pigment for yellow, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10,
11, 12, 13, 14, 15, 16, 17, 23, 6
5, 73, 83, C.I. I. Bat Yellow 1,3,20
And the like.

The amount of the colorant used is 0.1 to 60 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the binder resin.
0 parts by weight.

Further, in the present invention, one or more releasing agents may be contained in the toner, if necessary.

The release agent used in the present invention includes the following. Aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax and paraffin wax can be mentioned.

Here, the aliphatic hydrocarbon wax can be obtained, for example, by thermally decomposing a low molecular weight alkylene polymer obtained by radical polymerization of alkylene under high pressure or by a Ziegler catalyst under low pressure, or a high molecular weight alkylene polymer. A wax such as a synthetic hydrocarbon obtained by a hydrogenation of a hydrocarbon distillation residue obtained by an Arge process from a synthesis gas composed of an alkylene polymer, carbon monoxide, and hydrogen can be used. Further, those obtained by separating a hydrocarbon wax by use of a press sweating method, a solvent method, vacuum distillation, or a fractional crystallization method can be used. Further, as an example of the aliphatic hydrocarbon wax used in the present invention, in the DSC curve measured by a differential scanning calorimeter, with respect to the endothermic peak at the time of temperature rise and the exothermic peak at the time of temperature decrease, the endothermic onset temperature Is in the range of 50 to 110 ° C, and the temperature is 70 to 130 ° C.
An aliphatic hydrocarbon wax having at least one endothermic peak in the above region and having a maximum exothermic peak at the time of lowering the temperature within the range of the peak temperature of the endothermic peak ± 9 ° C. The hydrocarbon as a base is one synthesized by the reaction of carbon monoxide and hydrogen using a metal oxide catalyst (often two or more multi-component system), for example, the gintol method,
Hydrocarbons (using a fluidized catalyst bed) or Arge's method (using a fixed catalyst bed) where a large amount of waxy hydrocarbons can be obtained, and hydrocarbons with carbon numbers up to several hundred and alkylene such as ethylene are Ziegler Hydrocarbons polymerized with a catalyst can be used. Further, a wax synthesized by a method that does not depend on the polymerization of alkylene can be used.

Further, as the release agent used in the present invention, oxides of aliphatic hydrocarbon wax such as oxidized polyethylene wax or block copolymers thereof; fatty acids such as carnauba wax and montanic acid ester wax. Waxes containing an ester as a main component and fatty acid esters such as deoxidized carnauba wax obtained by deoxidizing a part or all of them can be used. Further, saturated straight chain fatty acids such as palmitic acid, stearic acid, and montanic acid, unsaturated fatty acids such as brundic acid, eleostearic acid, and vinalinaric acid, stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubayl alcohol, ceryl. Alcohols, saturated alcohols such as melicyl alcohol, polyhydric alcohols such as sorbitol, fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide, methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebis Saturated fatty acid bisamides such as lauric acid amide and hexamethylene bisstearic acid amide, ethylene bis oleic acid amide, hexamethylene bis oleic acid amide, N, N'-dioleyl adipic acid amide, N, N ' Unsaturated fatty acid amides such as dioleyl sebacic acid amide, aromatic bisamides such as m-xylene bisstearic acid amide, N, N′-distearyl isophthalic acid amide, calcium stearate, calcium laurate, zinc stearate, Fatty acid metal salts such as magnesium stearate (generally called metal soap), waxes obtained by grafting aliphatic hydrocarbon waxes with vinyl monomers such as styrene and acrylic acid, and behenin. Examples thereof include partial esterified products of fatty acids such as acid monoglyceride and polyhydric alcohols, and methyl ester compounds having a hydroxyl group obtained by hydrogenation of vegetable oils and the like.

Examples of the wax which is particularly preferably used in the present invention include aliphatic alcohol wax and alkyl monocarboxylic acid wax.

The aliphatic alcohol wax is represented by the following formula (2).

CH ₃ (CH ₂ ) _x CH ₂ OH (x = 20 to 250) Formula (2) The alkyl monocarboxylic acid wax is represented by the following formula (3).

CH ₃ (CH ₂ ) _y CH ₂ COOH (y = 20 to 250) Formula (3) The amount of the release agent used in the present invention is 0.1 to 20 parts by weight per 100 parts by weight of the binder resin. , Preferably 0.5 to 10
Parts by weight are desirable.

These releasing agents are usually contained in the binder resin by dissolving the resin in a solvent, increasing the temperature of the resin solution, and adding and mixing while stirring, or by mixing at the time of kneading.

As the negatively chargeable fluidizing agent used in the present invention, any agent can be used as long as the fluidity can be increased by adding it to the colorant-containing resin particles before and after the addition. It is possible. For example, fluororesin powders such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder, fine powder silica such as wet-process silica, dry-process silica, etc .; these silicas as silane coupling agents, titanium coupling agents, silicone oils, etc. And the like, surface-treated silica.

Preferred fluidizing agents are fine powders produced by the vapor phase oxidation of silicon halide compounds.
It is what is called dry silica or fumed silica, and is manufactured by a conventionally known technique. For example, it utilizes the thermal decomposition oxidation reaction of silicon tetrachloride gas in an oxyhydrogen flame, and the basic reaction formula is as follows.

SiCl ₄ + 2H ₂ + O ₂ → SiO ₂ + 4HCl

In this production process, it is also possible to obtain a composite fine powder of silica and another metal oxide by using another metal halide such as aluminum chloride or titanium chloride together with a silicon halide. Is also included. The particle size is desirably in the range of 0.001 to 2 μm as an average primary particle size, and it is particularly preferable to use silica fine powder in the range of 0.002 to 0.2 μm. .

The commercially available silica fine powder produced by vapor phase oxidation of a silicon halide used in the present invention includes, for example, those commercially available under the following trade names.

AEROSIL (Aerosil Japan) 130 200 300 380 TT600 MOX170 MOX80 COK84 Ca-O-SiL (CABOT Co.) M-5 MS-7 MS-75 HS-5 EH-5 Wacker HDK N20 V15 WAC -CHEMIE GMBH) N20E T30 T40 DC Fine Silica (Dow Corning Co.) Fransol (Fransil)

Further, it is more preferable to use treated silica fine powder obtained by subjecting silica fine powder generated by vapor-phase oxidation of the silicon halide to hydrophobic treatment. It is particularly preferable that the treated silica fine powder is obtained by treating the silica fine powder such that the degree of hydrophobicity measured by a methanol titration test shows a value in the range of 30 to 80.

The method for imparting hydrophobicity is provided by chemically treating an organic silicon compound or the like which reacts or physically adsorbs with the fine silica powder. As a preferred method, silica fine powder produced by vapor phase oxidation of a silicon halide is treated with an organosilicon compound.

Examples of such organosilicon compounds include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyl Dimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, ρ-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxy Silane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyl Disiloxane, 1,3-diphenyltetramethyldisiloxane and 2 to 12 per molecule
For example, dimethylpolysiloxane having a hydroxyl group bonded to Si and having one siloxane unit as a terminal unit may be used. These are used alone or as a mixture of two or more.

As the positively chargeable fluidizing agent used in the present invention, the above-mentioned dry process silica treated with a coupling agent having an amino group or silicone oil as described below is used.

[0115]

Embedded image

[0116]

Embedded image

As the silicone oil, an amino-modified silicone oil having a partial structure having an amino group in the side chain of the following formula is generally used.

[0118]

Embedded image

(Wherein R ₁ represents hydrogen, an alkyl group, an aryl group or an alkoxy group, R ₂ represents an alkylene group or a phenylene group, and R ₃ and R ₄ represent hydrogen, an alkyl group or an aryl group. However, the above alkyl group,
The aryl group, alkylene group and phenylene group may contain an amine, and may have a substituent such as halogen within a range not impairing the charging property. m and n represent positive integers. )

Examples of the silicone oil having such an amino group are as follows.

Viscosity at 25 ° C. Amine equivalent Product name (cps) SF8417 (Tore Silicone Co., Ltd.) 1200 3500 KF393 (Shin-Etsu Chemical Co., Ltd.) 60 360 KF857 (Shin-Etsu Chemical Co., Ltd.) 70 830 KF860 (Shin-Etsu Chemical Co., Ltd.) 250 7600 KF861 (Shin-Etsu Chemical Co., Ltd.) 3500 2000 KF862 (Shin-Etsu Chemical Co., Ltd.) 750 1900 KF864 (Shin-Etsu Chemical Co., Ltd.) 1700 3800 KF865 (Shin-Etsu Chemical Co., Ltd.) 90 4400 KF369 (Shin-Etsu Chemical Co., Ltd.) 20 320 KF383 (Shin-Etsu Chemical Co., Ltd.) 20 320 X-22-3680 (manufactured by Shin-Etsu Chemical Co., Ltd.) 90 8800 X-22-380D (manufactured by Shin-Etsu Chemical Co., Ltd.) 2300 3800 X-22-3801C (manufactured by Shin-Etsu Chemical Co., Ltd.) 3500 3800 X-22-2830B (manufactured by Shin-Etsu Chemical Co., Ltd.) Shin-Etsu Gakusha, Ltd.) 1300 1700

The amine equivalent is the equivalent per amine (g / eqiv) and is the value obtained by dividing the molecular weight by the number of amines per molecule.

The fluidizing agent used in the present invention has a specific surface area of 30 m ² / g or more, preferably 50 m ² / g or more by nitrogen adsorption measured by the BET method, which gives good results. Fluidizer 0.01 for 100 parts by weight of toner
To 8 parts by weight, preferably 0.1 to 4 parts by weight.

In order to prepare the toner of the present invention, a binder resin, a colorant and / or a magnetic material, a charge control agent or other additives are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill, and a kneader or an extruder is used. It is possible to obtain colored particles by melting, kneading and kneading a resin using a heat kneader such as a ruder to make the resins compatible with each other, cooling and solidifying the melt kneaded product, crushing the solidified product, and classifying the crushed product. it can.

Further, the fluidizing agent charged to the same polarity as the colored particles and the colored particles are sufficiently mixed by a mixing machine such as a Henschel mixer to obtain the toner of the present invention having the additive on the surface of the colored particles.

The method for measuring the properties of the binder resin according to the present invention is as follows.

(1) Fractionation of Binder Resin and Toner by Preparative Liquid Chromatography: Fractionation of Molecular Weight Range of 2000 to 50000 and Molecular Weight of 100,000 or More Fractions in the range of 2000 to 50,000 as well as in the range of molecular weight of 100,000 or more are collected by Nippon Analytical Industry Co., Ltd. Recycle Preparative HPLC LC-908.
Performed using a mold.

The sample of the preparative liquid chromatograph is prepared, for example, as follows.

The sample and chloroform were mixed and allowed to stand at room temperature for several hours (for example, 5 to 6 hours), then shaken well and the chloroform and sample were mixed well (until the unity of the sample disappeared), and further to room temperature. Let stand for 12 hours or more (for example, 24 hours). At this time, the time from the start of mixing the sample and chloroform to the end of the standing should be 24 hours or more. After that, a sample processing filter (pore size 0.45 to 0.5 μm, for example, Maisori Disc H-25-2 manufactured by Tosoh Corporation, Excicro Disc 25)
CR Gelman Science Japan Co., Ltd. is preferably used) as a sample of the preparative liquid chromatograph.

In the preparative liquid chromatogram, the preparative column JA is a preparative column JA manufactured by Nippon Analytical Industry Co., Ltd.
IGEL-1H, JAIGEL-2H, JAIGEL-
3H, JAIGEL-4H, JAIGEL-LS25
5, a preparative column selected from JAIGEL-5H and JAIGEL-6H is used.

(2) Measurement of weight average molecular weight and radius of gyration by light scattering method In the present invention, the weight average molecular weight and radius of gyration were measured by the static light scattering method. As the measuring device, a light scattering photometer DLS-700 manufactured by Otsuka Electronics Co., Ltd. was used. Further, in the molecular weight measurement by the static light scattering method, it is necessary to measure the rate of change (dn / dc) of the differential refractive index of the sample with respect to the sample concentration, and the measurement of dn / dc is made by Otsuka Electronics Co., Ltd. A refractometer DRM-1020 was used. The measurement procedure was performed by the following procedure as an example.

The resin and toner to be measured are dissolved in THF or chloroform, left to stand overnight, and the concentration of the sample filtered with a 0.2 μm filter is adjusted. For this concentration-adjusted sample, change the scattered light intensity and measurement angle,
The weight average molecular weight and the radius of gyration were determined from the formulas shown below.

Here, weight average molecular weight (M), second virial coefficient (A ₂ ), radius of gyration (S), concentration of solution (C)
so,

[0134]

(Equation 3)

The weight average molecular weight (M) and the radius of gyration (S) were calculated from the formula (I).

(3) Measurement of molecular weight by GPC method In the present invention, the molecular weight distribution of the chromatogram of the resin and toner by GPC method (gel permeation chromatography) is measured under the following conditions.

The measurement sample is prepared as follows.

The sample and THF (tetrahydrofuran) were mixed at a concentration of about 0.5 to 5 mg / ml (for example, about 5 mg / ml), and the mixture was allowed to stand at room temperature for several hours (for example, 5 to 6 hours), and then thoroughly mixed. Shake well mix the THF with the sample (until the samples are no longer coalesced) and let stand at room temperature for 12 hours or more (for example, 24 hours). At this time, the time from the start of mixing the sample and THF to the end of the standing is set to 24 hours or more. After that, the one that passed through a sample processing filter (pore size 0.45 to 0.5 μm, for example, Mysholydisk H-25-2 manufactured by Tosoh Corporation, Excicrodisk 25CR Gelman Science Japan Co., Ltd. can be preferably used) was passed through GPC. Of the sample. Sample concentration of resin component is 0.5-5 mg / ml
Adjust so that

In the GPC measuring apparatus, the column was stabilized in a heat chamber at 40 ° C., and THF as a solvent was flowed through the column at this temperature at a flow rate of 1 ml / min to obtain T
Approximately 100 μl of the HF sample solution is injected for measurement. When measuring the molecular weight of a sample, the molecular weight distribution of the sample
It is calculated from the relationship between the logarithmic value of the calibration curve prepared from several kinds of monodisperse polystyrene standard samples and the count number. A standard polystyrene sample for preparing a calibration curve has a molecular weight of 10 ² to 10 ⁷ manufactured by Tosoh Corporation or Showa Denko KK, for example.
It is suitable to use a standard polystyrene sample having at least about 10 points. RI for the detector
A (refractive index) detector is used. As the column, a plurality of commercially available polystyrene gel columns are preferably combined. For example, a Shodex GPC K manufactured by Showa Denko KK
F-801, 802, 803, 804, 805, 80
6,807,800P combination and Tosoh T
SKgel G1000H (H _XL ), G2000H
(H _XL ), G3000H (H _XL ), G4000H
(H _XL ), G5000H (H _XL ), G6000H
(H _XL ), G7000H (H _XL ), TSK guard
A combination of columns can be mentioned.

Generally, in the measurement of GPC chromatogram, the measurement starts from the baseline at which the chromatogram rises from the baseline on the high molecular weight side, and the molecular weight up to about 400 on the low molecular weight side.

Molecular weight 20 in GPC chromatogram
The abundance ratio of the region of 00 to 50000 can be calculated by obtaining the ratio of the integrated value of the region of molecular weight 2000 to 50000 to the integrated value of the chromatogram. Alternatively, the chromatogram of GPC was cut out and the cut-out G
Measure the total weight of the PC chromatogram to obtain a molecular weight of 200
Cut the area from 0 to 50,000 and measure the weight,
By determining the ratio of C to the total weight of the chromatogram, the abundance ratio of the region having a molecular weight of 2000 to 50000 can be determined.

(4) Glass transition temperature Tg Differential thermal analysis analyzer (DSC analyzer), DSC-7
(Perkin Elmer).

The measurement sample is 5 to 20 mg, preferably 10
Weigh the mg precisely. This is placed in an aluminum pan, and an empty aluminum pan is used as a reference, and measurement is performed at a temperature rising rate of 10 ° C./min at a measurement temperature range of 30 to 200 ° C. under normal temperature and normal humidity. During this temperature raising process, the temperature of 40 to 10
The endothermic peak of the main peak in the range of 0 ° C is obtained. At this time, the intersection of the line at the midpoint of the baseline before and after the appearance of the endothermic peak and the differential heat curve is taken as the glass transition temperature Tg in the present invention.

(5) Method for measuring acid value / OH value 1) Acid value A sample is precisely weighed, dissolved in a mixed solvent and water is added. The acid value of this solution is determined by potentiometric titration with 0.1N-NaOH using a glass electrode (according to JIS K1557-1970).

In the molecular weight distribution measurement, the acid value of the developer is measured in the same manner as described above by attaching a device for fractionation, drying the fractionated sample, and drying the sample.

2) OH number The sample is precisely weighed in a 100 ml round-bottomed flask, and 5 ml of the acetylating reagent is correctly added to this. Then 100 ° C ± 5
Dip in a bath at ℃ and heat. After 1-2 hours, the flask is taken out of the bath and allowed to cool, then water is added and shaken to decompose acetic anhydride. To further complete the decomposition, the flask is again heated in the bath for 10 minutes or more and allowed to cool, and then the wall of the flask is thoroughly washed with an organic solvent. This solution is subjected to potentiometric titration with an N / 2 potassium hydroxide ethyl alcohol solution using a glass electrode to determine the hydroxyl value. (According to JIS K0070-1966).

[0147]

EXAMPLES The present invention will be described below with reference to production examples and examples. Parts mean parts by weight.

(Resin Production Example 1) Synthesis of Branched Chain Polymer 1

[0149]

Embedded image Was placed in a glass reaction vessel, the inside of the vessel was sufficiently replaced with nitrogen, and the vessel was sealed. A 400 W ultraviolet lamp was placed 15 cm away from the reactor and reacted for 15 hours. After that, the irradiation of ultraviolet rays was stopped, 28 parts of divinylbenzene was added to the reaction vessel, the mixture was sufficiently stirred, and then ultraviolet rays were irradiated again to react for 20 minutes. In the molecular weight measurement of the obtained resin by the GPC method, the number average molecular weight Mn = 2,500 and the weight average molecular weight M
It was a resin having a glass transition temperature Tg of 60 ° C. at w = 5800. The resin obtained here is referred to as a resin a.

[0150] The measured infrared spectrum of this resin using FT-IR, near 910 cm ^-1,
An absorption peak due to the CH out-of-plane bending vibration of the CH ₂ ═CH-double bond terminal olefin was observed. In addition, when the residual monomer in the resin was analyzed by gas chromatography, divinylbenzene was not detected. From the above, in the obtained resin, one vinyl bond of divinylbenzene remains as it is, and the other vinyl bond is a resin bonded with a copolymer of styrene-n-butyl acrylate-monobutyl maleate ester. Is supposed to be.

Synthesis of Branched-Chain Polymer 2 A resin having a double bond at the terminal of the molecular chain was obtained in the same manner as the resin a except that the amount of the initiator and divinylbenzene were reduced. When the molecular weight of this resin was measured by the GPC method, the number average molecular weight was Mn = 4500, the weight average molecular weight was Mw = 7500, and the glass transition temperature Tg was 61 ° C. The resin obtained here is referred to as a resin b.

Synthesis of Binder Resin Styrene 85 parts n-butyl acrylate 15 parts Benzoyl peroxide 6 parts Toluene 200 parts were placed in a reactor and polymerized at 80 ° C. for 10 hours. Immediately after the start of the reaction, 100 parts of a toluene solution of the resin a (5 wt% solution) was added 4 times in total at an interval of 20 minutes to cause a polymerization reaction. The resin obtained here is referred to as a resin c. GP of resin c
In the molecular weight measurement by the C method, the number average molecular weight Mn =
5,200, the weight average molecular weight Mw was 12,800, and the glass transition temperature Tg was 60 ° C.

Styrene 75 parts n-butyl acrylate 25 parts Ditertiary butyl peroxide 2 parts Toluene 200 parts was used, and the addition amount of the resin b once was set to 80 parts, and the total amount was 320.
Resin d was obtained by synthesizing in the same manner as resin c except that part was added. In the molecular weight measurement of the resin d by the GPC method, the number average molecular weight Mn = 85,000 and the weight average molecular weight Mw = 2.
At 60,000, the glass transition temperature Tg was 58 ° C.

Resin 1 was obtained by mixing a toluene solution of the resins so that the weight ratio of the resins c and d was 75:25, and then removing and drying the toluene. When the molecular weight of this resin 1 was measured by the GPC method, the molecular weight was 130.
It had peaks at 00 and 250,000 and had a glass transition temperature Tg = 59 ° C.

Here, the binder resin component A ₁ having a molecular weight of 2,000 to 50,000 and the binder resin component B having a molecular weight of 100,000 or more, which were separated from the resin 1 by a preparative liquid chromatograph.
_{When the} weight average molecular weight and the radius of gyration of 1 were measured by the light scattering method, the following results were obtained.

[0156]

[Table 1]

Next, the synthesis was performed in the same manner as in the resins c and d except that the resin a and the resin b were not used and the peroxide was reduced, and the number average molecular weight Mn was measured by the GPC method.
6000, a resin e having a weight average molecular weight Mw of 20,000,
And number average molecular weight Mn = 95,000, weight average molecular weight M
Resin f of w = 320,000 was obtained.

Resin 1- (0) was obtained by mixing a toluene solution of the resin so that the weight ratio of the resin e and the resin f was 75:25, and then removing toluene and drying.
Here, with respect to Resin 1- (0), a binder resin component A ₀ having a molecular weight of 2,000 to 50,000 and a binder resin B ₀ having a molecular weight of 100,000 or more, which were separated by a preparative liquid chromatograph, were weight-averaged by a light scattering method. When the inertia radius was measured, the following results were obtained.

[0159]

[Table 2]

Here, A ₀ is a linear binder resin component having the same weight average molecular weight as A ₁ as measured by a light scattering method, and similarly B ₀ is a weight average molecular weight as measured by a light scattering method. It is a linear binder resin component having the same molecular weight as B ₁ . In the formula (1), n _{A 1 / A 0} and n _{B 1 / B 0} are n _{A 1 / A 0} = 3.
9, n _{B 1 / B 0} = 8.9.

[0161] (Resin Production Example 2) Styrene 84 parts of acrylic acid n- butyl, 11 parts 1,2,4-trivinylcyclohexane 5 parts _{(C 6 H 9 (CH =} CH 2) 3) di - data - Shall butylperoxide Oxide 0.8 parts Xylene 200 parts was put in a reactor, and the inside of the reactor was sufficiently replaced with nitrogen.
Polymerization was initiated at 44 ° C. Three hours after the initiation of polymerization, xylene was removed while raising the temperature to 200 ° C. under reduced pressure.
This resin is referred to as resin 2. In the measurement of the molecular weight of the obtained resin by the GPC method, the number average molecular weight Mn = 543
0, weight average molecular weight Mw = 11200, Tg = 5
9 ° C.

(Resin Production Example 3) Styrene 71 parts N-butyl acrylate 24.7 parts Maleic acid monobutyl ester 4 parts Divinylbenzene 0.03 parts Benzoyl peroxide 0.15 parts

170 parts of water in which 0.12 parts of partially saponified polyvinyl alcohol was dissolved was added to the above mixed solution, and the mixture was vigorously stirred to give a suspension dispersion. The above suspension dispersion was added to a reactor in which 500 parts of water was charged and the atmosphere was replaced with nitrogen.
The suspension polymerization reaction was carried out for 8 hours. After the reaction was completed, it was washed with water, dehydrated and dried to obtain a resin 3. In the molecular weight measurement of the obtained resin by the GPC method, the number average molecular weight Mn = 24.
The weight average molecular weight was 70,000, Mw was 14,780,000, and the glass transition temperature Tg was 60.3 ° C.

(Resin Production Example 4) Resin 2 was obtained by mixing resin 2 and resin 3 with a xylene solution of the resin in a weight ratio of 4: 1, and then removing xylene and drying.
In measuring the molecular weight of the obtained resin by the GPC method,
Number average molecular weight Mn = 6170, weight average molecular weight Mw = 2
It was 83000 and the glass transition temperature Tg was 60 ° C.

(Resin Production Example 5) Synthesis of Low Molecular Weight Polyester Resin Fumaric acid 23 mol% Trimellitic anhydride 30 mol% Bisphenol derivative represented by the formula (a) 47 mol% (R: propylene group x + y = 2.2)

By condensation-polymerizing these, there is no gel content and GP
In the molecular weight measurement by the C method, the number average molecular weight Mn = 3
A polyester resin i having a glass transition temperature Tg of 60 ° C. and a weight average molecular weight Mw of 12,000 of 800 was obtained.

Synthesis of high molecular weight polyester resin Fumaric acid 48 mol% Bisphenol derivative represented by the formula (a) 52 mol% (R: propylene group x + y = 2.2)

In the molecular weight measurement by GPC method by condensation polymerization of these, the number average molecular weight Mn = 2500, the weight average molecular weight Mw = 8000, and the glass transition temperature Tg = 5.
Polyester resin j at 2 ° C. was obtained. The number average molecular weight Mn was 9500 and the weight average molecular weight Mw was the same as that of the resin j, but the reaction time was changed and the molecular weight was measured by the GPC method.
= 28,000, a polyester resin k having a glass transition temperature Tg = 60 ° C. was obtained. j and k were mixed at a weight ratio of 2: 1 and further added so that the amount of trimellitic anhydride was 10 mol%, condensation polymerization was performed, and there was no gel content, and the number average molecular weight was measured by the GPC method. Mn = 1100
A polyester resin 1 having a weight average molecular weight Mw of 48,000 and a glass transition temperature Tg of 60 ° C. was obtained. The polyester resins i and 1 were mixed in a weight ratio of 4: 6, and the number average molecular weight Mn was 9000 and the weight average molecular weight Mw was 43000 in the measurement of the molecular weight by the GPC method.
Resin 5 having a glass transition temperature Tg = 60 ° C. was obtained.

Here, as for Resin 5, as in Resin Production Example 1, a binder resin component A ₃ having a molecular weight of 2000 to 50000,
The binder resin component B ₃ having a molecular weight of 100,000 or more was collected by a preparative liquid chromatograph, the weight average molecular weight and the radius of gyration were measured by the light scattering method, and the molecular weight was measured by the GPC method. The following results were obtained.

[0170]

[Table 3]

Resin Production Example 6 In Resin Production Example 5,
By changing the composition ratio, reaction time, and blend ratio, G
In the molecular weight measurement by the PC method, the number average molecular weight Mn =
Resin 6 having a glass transition temperature Tg of 58 ° C. and a weight average molecular weight Mw of 8500 was obtained.

(Resin Production Example 7) The same procedure as in Resin Production Example 5 was carried out, and the number average molecular weight Mn was 3500 and the weight average molecular weight Mw was 55000 in the molecular weight measurement by GPC method.
Resin 7 having a glass transition temperature Tg = 60 ° C. was obtained.

(Resin Production Example 8) Terephthalic acid 22 mol% Dodecenylsuccinic acid 21 mol% Trimellitic anhydride 7 mol% Bisphenol derivative represented by the formula (a) 18 mol% (R: propylene group x + y = 2.2) Formula (a) 32 mol% of a bisphenol derivative represented by (R: ethylene group x + y = 2.2)

These were subjected to condensation polymerization, and the number average molecular weight Mn was 3340, the weight average molecular weight Mw was 47800, and the glass transition temperature Tg was 5 in the molecular weight measurement by the GPC method.
Resin 8 at 9 ° C. was obtained.

(Resin Production Example 9) Terephthalic acid 20 mol% Trimellitic anhydride 30 mol% Bisphenol derivative represented by the formula (a) 50 mol% (R: propylene group x + y = 2.2)

These were subjected to condensation polymerization, and the number average molecular weight Mn was 10700, the weight average molecular weight Mw was 168000, and the glass transition temperature Tg was measured by the GPC method.
= 59 ° C Resin 9 was obtained.

(Resin Production Example 10) Fumaric acid 50 mol% Bisphenol derivative represented by the formula (a) 50 mol% (R: propylene group x + y = 2.2)

In the molecular weight measurement by GPC method by condensation polymerization of these, number average molecular weight Mn = 1050, weight average molecular weight Mw = 31700, glass transition temperature Tg = 5.
Resin 10 at 9 ° C. was obtained.

(Resin Production Example 11) Styrene 70 parts n-Butyl acrylate 25 parts Maleic acid monobutyl ester 5 parts 2,2-bis (4,4-di-tert-butyl-butyl 0.1 part Peroxycyclohexyl ) Propane Benzoyl peroxide 0.1 part

Polymerization was carried out by suspension polymerization, and a resin m having a number average molecular weight Mn of 380,000, a weight average molecular weight Mw of 950,000 and a glass transition temperature Tg of 59 ° C. was obtained by the GPC method. The resin e obtained in Resin Production Example 1 and this resin m were mixed with a toluene solution of the resin so that the weight ratio was 75:25, and then toluene was removed and dried to obtain a resin 11.

(Resin Production Example 12) i was used as the low molecular weight polyester resin, and the binder resin 1 was prepared by changing the composition ratio, reaction time, and blend ratio during the synthesis of the high molecular weight polyester.
2 was obtained.

The characteristic values of the above resins 1 to 12 are summarized in Table 4.

[0183]

[Table 4] 1) Peak position: 13000, 250,000 2) Peak position: 10700, 888000 3) Peak position: 17,000, 465,000

Example 1 Resin 6 100 parts Magnetic iron oxide 90 parts (Average particle size 0.15 μm, Hc115 oersted, σs80 emu / g, σr11 emu / g) Release agent a 5 parts [Aliphatic alcohol wax CH ₃ (CH ₂ ) _x CH ₂ OH (x = 48, OH value = 70)] Monoazo metal complex (negative charge controlling agent) 2 parts

The above materials were premixed with a Henschel mixer, and then melt-kneaded at 130 ° C. with a twin-screw kneading extruder. After allowing the kneaded product to cool, after roughly crushing with a cutter mill,
The particles were pulverized with a fine pulverizer using a jet stream and further classified with an air classifier to obtain magnetic colored particles having a weight average particle diameter of 6.5 μm. For 100 parts of these magnetic colored particles,
A developer was prepared by externally adding 1.0 part of hydrophobic dry silica (BET 300 m ^{2 /} g) with a Henschel mixer.

Using this developer, image characteristics were evaluated with a digital copying machine GP-55 manufactured by Canon, and good results were obtained as shown in Table 5. The GP-55 fixing device was removed, the external drive and temperature control functions were added, the fixing speed was changed, and a fixing test was conducted.
Good results were obtained as shown in.

In the image characteristic evaluation, the density gradation was good. Furthermore, even after copying 20,000 sheets, the phenomenon of so-called selective development in which only the developer with a small particle size is developed and consumed does not occur, the halftone image quality is almost the same as the initial stage, there is no uneven density, and it is smooth and good. It was a thing.

<Examples 2 to 11> Good results were obtained in the same manner as in Example 1 except that the binder resin and the release agent were changed as shown in Table 5. Further, the grain size after copying 20,000 sheets was almost the same as the initial grain size, and good image characteristics were obtained.

<Comparative Examples 1 and 2> The same procedure as in Example 1 was carried out except that the binder resin was changed as shown in Table 5, and the results as shown in Table 5 were obtained.

In this example, the following wax b was used as a release agent. The wax b is produced by the Arge method.
It is obtained by fractional crystallization from the synthesized hydrocarbon wax. The DSC characteristic of the wax b in the present invention was measured according to the following procedure.

In the DSC measurement of the wax in the present invention, the heat exchange is measured and the behavior thereof is observed. Therefore, from the measurement principle, it is necessary to measure with a highly accurate internal heat input compensation type differential scanning calorimeter. For example, DSC-7 manufactured by PerkinElmer can be used.

The measuring method is ASTM D3418-82.
Perform according to. The DSC curve used in the present invention has a temperature rate of 10 ° C./min after the temperature is raised once and a previous history is taken.
A DSC curve measured when the temperature is lowered and raised in a temperature range of 0 to 200 ° C. is used. The definition of each temperature is defined as follows.

Endothermic peak of wax (endothermic in the positive direction) Onset temperature (OP) of endothermic wax: the tangent of the curve at the lowest temperature of the peak curve differential values Temperature at the intersection of the tangent line and the base line Wax endothermic peak temperature (PP): Peak top temperature

Wax exothermic peak (minus direction is assumed to be exothermic) Wax exothermic peak temperature: temperature at peak top of maximum peak

When DSC measurement of the wax b was carried out, the onset temperature at the time of temperature increase was 67 ° C., the endothermic peak temperature at the time of temperature increase was 105 ° C., and the maximum exothermic peak temperature at the time of temperature decrease was 103 ° C. It was ℃. DSC of wax b
The characteristics are shown in FIGS.

[0196]

[Table 5] 1) Good ← ○, ○ △, △, △ ×, × → Evaluated in 5 grades. 2) Environmental stability was evaluated by images after standing for 24 hours under high temperature (30 ° C.) and high humidity (85%). 3) The temperature in the table is the fixing start temperature. The rate of reduction of the rubbing density of the fixed image of 10% or less was evaluated as the fixing area.

[0197]

The following effects can be obtained by using the toner of the present invention.

(1) It is possible to provide a toner having good fixing property and anti-offset property from low speed to high speed copying machines.

(2) It is possible to provide a toner having good fixing property and good image quality in the halftone portion from low speed to high speed copying machine.

(3) It is possible to provide a toner excellent in environmental stability without being affected by environmental changes.

(4) It is possible to provide a toner having a good image density and a good density gradation.

[Brief description of the drawings]

FIG. 1 is a DSC curve of a wax b used in an example of the present invention at the time of heating.

FIG. 2 is a DSC curve when the temperature of the wax b used in the example of the present invention is lowered.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Makoto Unno 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (24)

[Claims] 1. A toner containing at least a binder resin and a colorant, wherein the binder resin or the toner has a molecular weight of 2000 to 500 fractionated by preparative liquid chromatography.
Binder resin component A in the area of 00 and molecular weight 100,000
The binder resin component B in the above range is expressed by the following formula (1) (In the formula (1), LM _A represents the weight average molecular weight of the binder resin component A measured by the light scattering method, and LM _B is the weight average molecular weight of the binder resin component B measured by the light scattering method. , S _A represents the radius of gyration of the binder resin component A measured by the light scattering method, and S _B represents the radius of gyration of the binder resin component B measured by the light scattering method). Toner characterized by: 2. The value of n _{A / B represented by} the formula (1) is 2 to 7.
The toner according to claim 1, wherein the toner is 0. 3. GP in the range of 2,000 to 50,000 in the molecular weight measured by gel permeation chromatography (GPC method) of toner or binder resin.
The toner according to claim 1 or 2, wherein an abundance ratio in a C chromatogram is 50 to 90%. 4. A polyester resin used as a binder resin has a number average molecular weight of 1,000 to 8,000 as measured by the GPC method.
0, the weight average molecular weight by GPC method is 5,000 to 100
4. The toner according to claim 1, wherein the toner is 00000. 5. A polyester resin used as a binder resin has a number average molecular weight of 1500 to 5000 by GPC method.
0, the weight average molecular weight by the GPC method is 10,000 to 50
4. The toner according to claim 1, wherein the toner is 00000. 6. The toner according to claim 1, wherein the polyester resin used as the binder resin has an acid value of 2 to 70. 7. The OH number of the polyester resin used as the binder resin is 50 or less.
7. The toner according to any one of 6 to 6. 8. A polyester resin obtained by subjecting a trivalent or higher carboxylic acid or alcohol to a condensation reaction without forming a gel is used as a resin for blending a binder resin. The toner according to claim 1. 9. A polyester resin obtained by subjecting a carboxylic acid or alcohol having a valence of 3 or more to 10 mol% or more and conducting a condensation reaction without forming a gel, is used as a resin for blending a binder resin. The toner according to any one of claims 1 to 7. 10. A polyester resin obtained by synthesizing a linear polyester, adding a carboxylic acid or alcohol having a valence of 3 or more, and further conducting a condensation reaction is used as a resin for blending a binder resin. The toner according to any one of claims 1 to 7. 11. A polyester-based resin obtained by separately synthesizing a non-linear polyester-based resin and a linear or non-linear polyester-based resin and then mixing them, is used as a binder resin. The toner according to any one of claims 1 to 7. 12. The vinyl-based resin used as the binder resin has a molecular weight of 20 when measured by GPC method.
4. The toner according to claim 1, which has at least one peak in the range of 00 to 100,000 and has at least one peak in a region exceeding 100,000. 13. A vinyl-based resin synthesized by synthesizing a branched-chain polymer having a double bond at an end and then adding the branched-chain polymer during polymerization of the main-chain polymer is used as a binder resin. 13. The toner according to claim 3 or claim 12. 14. The toner according to claim 1, wherein a vinyl resin synthesized using a monomer having three or more vinyl groups is used as a binder resin. 15. The toner according to claim 1, wherein the binder resin component A and the binder resin component B have a glass transition temperature of 50 to 80 ° C. 16. The toner according to claim 1, wherein the glass transition temperatures of the binder resin component A and the binder resin component B are 53 to 70 ° C. 17. The glass transition temperature of the binder resin is 50-8.
The toner according to any one of claims 1 to 14, which has a temperature of 0 ° C. 18. The glass transition temperature of the binder resin is 53 to 7.
The toner according to any one of claims 1 to 14, which has a temperature of 0 ° C. 19. The toner according to claim 1, wherein the binder resin component A and the binder resin component B have a branched chain weight average molecular weight of 300 to 80,000. 20. The toner according to claim 1, wherein the binder resin component A and the binder resin component B have a branched chain weight average molecular weight of 500 to 50,000. 21. The glass transition temperature Tgs of the main chain and the glass transition temperature Tgb of the side chain of the binder resin components A and B are | T
15. The toner according to claim 1, wherein gs-Tgb | ≦ 30 deg is satisfied. 22. The glass transition temperature Tgs of the main chain and the glass transition temperature Tgb of the side chain of the binder resin components A and B are | T.
15. The toner according to claim 1, wherein gs-Tgb | ≦ 20 deg is satisfied. 23. DS measured by a differential scanning calorimeter
Regarding the endothermic peak at the time of temperature rise and the exothermic peak at the time of temperature fall in the C curve, the endothermic onset temperature is in the range of 50 to 110 ° C., and at least 1 in the temperature range of 70 to 130 ° C.
There are two endothermic peaks, and the peak temperature of the endothermic peak ± 9
The toner according to any one of claims 1 to 22, wherein an aliphatic hydrocarbon wax having a maximum exothermic peak at the time of lowering the temperature in the range of ° C is used as a release agent. 24. The aliphatic alcohol wax or the alkyl monocarboxylic acid wax represented by the following formulas (2) and (3) is used as a mold release agent. Toner. Aliphatic alcohols _{wax: CH 3 (CH 2) x} CH 2 OH Formula (2) (x = 20~250) alkyl monocarboxylic acids _{wax: CH 3 (CH 2) y} CH 2 COOH formula (3) (y = 20-250)